Search

A photoacoustic detection module based on a gold-plated photoacoustic cell was reported in this manuscript to measure hydrogen sulfide (H2S) gas in sewers. A 1582 nm distributed feedback (DFB) diode laser was employed as the excitation light source of the photoacoustic sensor. Operating pressure within the photoacoustic cell and laser modulation depth were optimized at room temperature, and the long-term stability of the photoacoustic sensor system was analyzed by an Allan-Werle deviation analysis. Experimental results showed that under atmospheric pressure and room temperature conditions, the photoacoustic detection module exhibits a sensitivity of 11.39 μV/ppm of H2S and can reach a minimum detection limit (1σ) of 140 ppb of H2S with an integration time of 1 s. The sensor was tested for in-field measurements by sampling gas in the sewer near the Shanxi University canteen: levels of H2S of 81.5 ppm were measured, below the 100 ppm limit reported by the Chinese sewer bidding document.

We report on a comparison between two optical detection techniques, one based on a Quartz-Enhanced Photoacoustic Spectroscopy (QEPAS) detection module, where a quartz tuning fork is acoustically coupled with a pair of millimeter-sized resonator tubes; and the other one based on a Photothermal Spectroscopy (PTS) module where a Fabry-Perot interferometer acts as transducer to probe refractive index variations. When resonant optical absorption of modulated light occurs in a gas sample, QEPAS directly detects acoustic waves while PTS probes refractive index variations caused by local heating. Compact QEPAS and PTS detection modules were realized and integrated in a gas sensor system for detection of carbon monoxide (CO), targeting the fundamental band at 4.6 μm by using a distributed-feedback quantum cascade laser. Performance was compared and ultimate detection limits up to ∼ 6 part-per-billion (ppb) and ∼15 ppb were reached for QEPAS and the PTS module, respectively, using 100 s integration time and 40 mW of laser power.

We demonstrated that quartz-enhanced photoacoustic spectroscopy (QEPAS) is an efficient tool to measure the vibrational relaxation rate of gas species, employing quartz tuning forks (QTFs) as sound detectors. Based on the dependence of the QTF resonance frequency on the resonator geometry, a wide range of acoustic frequencies with narrow detection bandwidth was probed. By measuring the QEPAS signal of the target analyte as well as the resonance properties of different QTFs as a function of the gas pressure, the relaxation time can be retrieved. This approach has been tested in the near infrared range by measuring the CH4 (nν4) vibrational relaxation rate in a mixture of 1% CH4, 0.15 % H2O in N2, and the H2O (ν1) relaxation rate in a mixture of 0.5 % H2O in N2. Relaxation times of 3.2 ms Torr and 0.25 ms Torr were estimated for CH4 and H2O, respectively, in excellent agreement with values reported in literature.

In this work, we report on a quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor for hydrogen sulfide (H2S) detection, exploiting a liquid-nitrogen-cooled THz quantum cascade laser (QCL) operating in pulsed mode. The spectrophone was designed to accommodate a THz QCL beam and consisted of a custom quartz tuning fork with a large prong spacing, coupled with acoustic resonator tubes. The targeted rotational transition falls at 2.87 THz (95.626 cm−1), with a line-strength of 5.53 ∙ 10-20 cm/mol. A THz QCL peak power of 150 mW was measured at a heat sink temperature of 81 K, pulse width of 1 μs and repetition rate of 15.8 kHz. A QEPAS record sensitivity for H2S detection in the THz range of 360 part-per-billion in volume was achieved at a gas pressure of 60 Torr and 10 s integration time.

A theoretical analysis and experimental investigation of the influence of gas pressure on resonance properties, namely, the quality factor and resonance frequency, of a T-shaped quartz tuning fork (QTF) is reported here. Two configurations are considered: a bare QTF, and a QTF coupled with a pair of resonator tubes (spectrophone). In both configurations, the effect of air on resonance frequency due to the additional inertia on prong motion and the influence of air damping on the quality factor, were analysed. By comparing the bare QTF and the spectrophone results, the effect of pressure on the acoustic coupling between the QTF and the tubes was theoretically modelled and then validated. The results show that acoustic coupling is strongly influenced by air pressure, leading to a shift of resonance frequency and a decrease in the quality factor up to 24%.

We report on a fiber-coupled, quartz-enhanced photoacoustic spectroscopy (QEPAS) near-IR sensor for sequential detection of methane (CH4 or C1) and ethane (C2H6 or C2) in air. With the aim of developing a lightweight, compact, low-power-consumption sensor suitable for unmanned aerial vehicles (UAVs)-empowered environmental monitoring, an all-fiber configuration was designed and realized. Two laser diodes emitting at 1653.7 nm and 1684 nm for CH4 and C2H6 detection, respectively, were fiber-combined and fiber-coupled to the collimator port of the acoustic detection module. No cross talk between methane and ethane QEPAS signal was observed, and the related peak signals were well resolved. The QEPAS sensor was calibrated using gas samples generated from certified concentrations of 1% CH4 in N2 and 1% C2H6 in N2. At a lock-in integration time of 100 ms, minimum detection limits of 0.76 ppm and 34 ppm for methane and ethane were achieved, respectively. The relaxation rate of CH4 in standard air has been investigated considering the effects of H2O, N2 and O2 molecules. No influence on the CH4 QEPAS signal is expected when the water vapor concentration level present in air varies in the range 0.6–3%.

Here we present a computational and experimental fluid dynamics study for the characterization of the flow field within the gas chamber of a Quartz-Enhanced Photoacoustic Spectroscopy (QEPAS) sensor, at different flow rates at the inlet of the chamber. The transition from laminar to turbulent regime is ruled both by the inlet flow conditions and dimension of the gas chamber. The study shows how the distribution of the flow field in the chamber can influence the QEPAS sensor sensitivity, at different operating pressures. When turbulences and eddies are generated within the gas chamber, the efficiency of photoacoustic generation is significantly altered., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Authors.)

We report on a photoacoustic sensor system based on a differential photoacoustic cell to detect the concentration of CO impurities in hydrogen. A DFB-QCL laser with a central wavelength of 4.61 µm was employed as an exciting source with an optical power of 21 mW. Different concentrations of CO gas mixed with pure hydrogen were injected into the photoacoustic cell to test the linear response of the photoacoustic signal to the CO concentration. The stability of the long-term operation was verified by Allan-Werle deviation analysis. The minimum detection limit (MDL, SNR=1) results 8 ppb at 1 s and reaches a sub-ppb level at 100 s of integration time. Dynamic response of the system is linear and has been tested up to the concentration of 6 ppm. Saturation conditions are expected to be reached for CO concentration larger than 100 ppm., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2024 The Authors.)

In this paper, an end-to-end methane gas detection algorithm based on transformer and multi-layer perceptron (MLP) for tunable diode laser absorption spectroscopy (TDLAS) is presented. It consists of a Transformer-based U-shaped Neural Network (TUNN) filtering algorithm and a concentration prediction network (CPN) based on MLP. This algorithm employs an end-to-end architectural design to extract information from noisy transmission spectra of methane and derive the CH 4 concentrations from denoised spectra, without intermediate steps. The results demonstrate the superiority of the proposed TUNN filtering algorithm over other typically employed digital filters. For concentration prediction, the determination coefficient (R 2 ) reached 99.7%. Even at low concentrations, R 2 remained notably high, reaching up to 89%. The proposed algorithm results in a more efficient, convenient, and accurate spectral data processing for TDLAS-based gas sensors.

In this work, we report on the novel employment of lithium niobate tuning forks as acoustic transducers in photoacoustic spectroscopy for gas sensing. The lithium niobate tuning fork (LiNTF) exhibits a fundamental resonance frequency of 39196.6 Hz and a quality factor Q = 5900 at atmospheric pressure. The possibility to operate the LiNTF as a photoacoustic wave detector was demonstrated targeting a water vapor absorption line falling at 7181.14 cm -1 (1.39 µm). A noise equivalent concentration of 2 ppm was reached with a signal integration time of 20 s. These preliminary results open the path towards integrated photonic devices for gas sensing with LiNTF-based detectors on lithium niobate platforms., (© 2023 The Authors.)

In this work, we report on the implementation of a multi-quantum cascade laser (QCL) module as an innovative light source for quartz-enhanced photoacoustic spectroscopy (QEPAS) sensing. The source is composed of three different QCLs coupled with a dichroitic beam combiner module that provides an overlapping collimated beam output for all three QCLs. The 3λ-QCL QEPAS sensor was tested for detection of NO 2 , SO 2 , and NH 3 in sequence in a laboratory environment. Sensitivities of 19.99 mV/ppm, 19.39 mV/ppm, and 73.99 mV/ppm were reached for NO 2 , SO 2 , and NH 3 gas detection, respectively, with ultimate detection limits of 9 ppb, 9.3 ppb, and 2.4 ppb for these three gases, respectively, at an integration time of 100 ms. The detection limits were well below the values of typical natural abundance of NO 2 , SO 2 , and NH 3 in air.

We present a quartz enhanced photoacoustic spectroscopy (QEPAS) gas sensor designed for precise monitoring of ammonia (NH 3 ) at ppb-level concentrations. The sensor is based on a novel custom quartz tuning fork (QTF) with a mid-infrared quantum cascade laser emitting at 9.55 µm. The custom QTF with a hammer-shaped prong geometry which is also modified by surface grooves is designed as the acoustic transducer, providing a low resonance frequency of 9.5 kHz and a high-quality factor of 10263 at atmospheric pressure. In addition, a temperature of 50 °C and a large gas flow rate of 260 standard cubic centimeters per minute (sccm) are applied to mitigate the adsorption and desorption effect arising from the polarized molecular of NH 3 . With 80-mW optical power and 300-ms lock-in integration time, the detection limit is achieved to be 2.2 ppb which is the best value reported in the literature so far for NH 3 QEPAS sensors, corresponding to a normalized noise equivalent absorption coefficient of 1.4 × 10 -8 W cm -1 Hz -1/2 . A five-day continuous monitoring for atmospheric NH 3 is performed, verifying the stability and robustness of the presented QEPAS-based NH 3 sensor., Competing Interests: The authors declare that there are no conflicts of interest., (© 2023 The Authors.)

We present an optical sensor based on light-induced thermoelastic spectroscopy for the detection of hydrogen sulfide (H 2 S) in sulfur hexafluoride (SF 6 ). The sensor incorporates a compact multi-pass cell measuring 6 cm × 4 cm × 4 cm and utilizes a quartz tuning fork (QTF) photodetector. A 1.58 µm near-infrared distributed feedback (DFB) laser with an optical power of 30 mW serves as the excitation source. The sensor achieved a minimum detection limit (MDL) of ∼300 ppb at an integration time of 300 ms, corresponding to a normalized noise equivalent absorption coefficient (NNEA) of 3.96 × 10 -9 W·cm -1 ·Hz -1/2 . By extending the integration time to 100 s, the MDL can be reduced to ∼25 ppb. The sensor exhibits a response time of ∼1 min for a gas flow rate of 70 sccm., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2023 The Authors.)

Here we report on a study of the non-radiative relaxation dynamic of 12 CH 4 and 13 CH 4 in wet nitrogen-based matrixes by using the quartz-enhanced photoacoustic spectroscopy (QEPAS) technique. The dependence of the QEPAS signal on pressure at fixed matrix composition and on H 2 O concentration at fixed pressure was investigated. We demonstrated that QEPAS measurements can be used to retrieve both the effective relaxation rate in the matrix, and the V-T relaxation rate associated to collisions with nitrogen and water vapor. No significant differences in measured relaxation rates were observed between the two isotopologues., Competing Interests: A conflicting interest exists when professional judgement concerning a primary interest (such as patient’s welfare or the validity of research) may be influenced by a secondary interest (such as financial gain or personal rivalry). It may arise for the authors when they have financial interest that may influence their interpretation of their results or those of others. Examples of potential conflicts of interest include employment, consultancies, stock ownership, honoraria, paid expert testimony, patent applications/registrations, and grants or other funding., (© 2023 The Authors.)

In this work, a comparison between Quartz Enhanced Photoacoustic Spectroscopy (QEPAS) and Beat Frequency-QEPAS (BF-QEPAS) techniques for environmental monitoring of pollutants is reported. A spectrophone composed of a T-shaped Quartz Tuning Fork (QTF) coupled with resonator tubes was employed as a detection module. An interband cascade laser has been used as an exciting source, allowing the targeting of two NO absorption features, located at 1900.07 cm -1 and 1900.52 cm -1 , and a water vapor absorption feature, located at 1901.76 cm -1 . Minimum detection limits of 90 ppb and 180 ppb were achieved with QEPAS and BF-QEPAS techniques, respectively, for NO detection. The capability to detect multiple components in the same gas mixture using BF-QEPAS was also demonstrated., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2023 The Authors.)

Quartz tuning forks (QTFs) are employed as sensitive elements for gas sensing applications implementing quartz-enhanced photoacoustic spectroscopy. Therefore, proper design of the QTF read-out electronics is required to optimize the signal-to-noise ratio (SNR), and in turn, the minimum detection limit of the gas concentration. In this work, we present a theoretical study of the SNR trend in a voltage-mode read-out of QTFs, mainly focusing on the effects of (i) the noise contributions of both the QTF-equivalent resistor and the input bias resistor R L of the preamplifier, (ii) the operating frequency, and (iii) the bandwidth (BW) of the lock-in amplifier low-pass filter. A MATLAB model for the main noise contributions was retrieved and then validated by means of SPICE simulations. When the bandwidth of the lock-in filter is sufficiently narrow (BW = 0.5 Hz), the SNR values do not strongly depend on both the operating frequency and R L values. On the other hand, when a wider low-pass filter bandwidth is employed (BW = 5 Hz), a sharp SNR peak close to the QTF parallel-resonant frequency is found for large values of R L (R L > 2 MΩ), whereas for small values of R L (R L < 2 MΩ), the SNR exhibits a peak around the QTF series-resonant frequency.

In this Letter, a side-excitation light-induced thermoelastic spectroscopy (SE-LITES) technique was developed for trace gas detection. A novel, to the best of our knowledge, custom quartz tuning fork (QTF) was used as a transducer for photon detection by the thermoelastic effect. The mechanical stress distribution on the QTF surface was analyzed to identify the optimum thermoelastic excitation approach. The electrode film on the QTF surface also works as a partially reflective layer to obtain a long optical absorption path inside the QTF body. With the long optical absorption length and the inner face excitation of the QTF, the thermoelastic effect was greatly enhanced. With an optimized modulation depth, a signal-to-noise ratio (SNR) improvement of more than one order of magnitude was achieved, compared to traditional LITES.

A gas sensor based on light-induced thermo-elastic spectroscopy (LITES) capable to detect methane (C1) and ethane (C2) in a wide concentration range, from percent down to part-per-billion (ppb), is here reported. A novel approach has been implemented, exploiting a compact sensor design that accommodates both a custom 9.8 kHz quartz tuning fork (QTF) used as photodetector and the gas sample in the same housing. The resulting optical pathlength was only 2.5 cm. An interband cascade laser (ICL) with emission wavelength of 3.345 µm was used to target absorption features of C1 and C2. The effects of high concentration analytes on sensor response were firstly investigated. C1 concentration varied from 1% to 10%, while C2 concentration varied from 0.1% to 1%. These ranges were selected to retrace the typical natural gas composition in a 1:10 nitrogen dilution. The LITES sensor was calibrated for both the gas species independently and returned nonlinear but monotonic responses for the two analytes. These univariate calibrations were used to retrieve the composition of C1-C2 binary mixtures with accuracy higher than 98%, without the need for further data analysis. Minimum detection limits of ∼650 ppb and ∼90 ppb were achieved at 10 s of integration time for C1 and C2, respectively, demonstrating the capability of the developed LITES sensor to operate with concentration ranges spanning over 6 orders of magnitude., Competing Interests: The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Angelo Sampaolo reports equipment, drugs, or supplies and travel were provided by Polytechnic University of Bari., (© 2023 The Authors.)

The increase in fatal accidents and chronic illnesses caused by hydrogen sulfide (H 2 S) exposure occurring in various workplaces is pushing the development of sensing systems for continuous and in-field monitoring of this hazardous gas. We report here on the design and realization of a Near-IR quartz-enhanced photoacoustic sensor (QEPAS) for H 2 S leaks detection. H 2 S QEPAS signal was measured in matrixes containing up to 1 % of methane (CH 4 ) and nitrogen (N 2 ) which were chosen as the laboratory model environment for leakages from oil and gas wells or various industrial processes where H 2 S and CH 4 can leak simultaneously. An investigation of the influence of CH 4 on H 2 S relaxation and photoacoustic generation was proposed in this work and the sensor performances were carefully assessed with respect to CH 4 content in the mixture. We demonstrated the high selectivity, with no cross talk between H 2 S, H 2 O and CH 4 absorption lines, high sensitivity, and fast response time of the developed sensor, achieving a minimum detection limit (MDL) of 2.5 ppm for H 2 S with 2 s lock-in integration time. The employed 2.6 µm laser allowed us to employ the sensor also for CH 4 detection, achieving an MDL of 85 ppm. The realized QEPAS sensor lends itself to the development of a portable and compact device for industrial monitoring., Competing Interests: The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Angelo Sampaolo reports equipment, drugs, or supplies and travel were provided by Polytechnic University of Bari., (© 2022 The Authors. Published by Elsevier GmbH.)

We report on the development of a highly sensitive hydrogen sulfide (H 2 S) gas sensor exploiting the doubly resonant photoacoustic spectroscopy technique and using a near-infrared laser emitting at 1578.128 nm. By targeting the R(4) transition of H 2 S, we achieved a minimum detection limit of 10 part per billion in concentration and a normalized noise equivalent absorption coefficient of 8.9 × 10 -12 W cm -1 Hz -1/2 . A laser-cavity-molecule locking strategy is proposed to enhance the sensor stability for fast measurement when dealing with external disturbances. A comparison among the state-of-the-art H 2 S sensors using various spectroscopic techniques confirmed the record sensitivity achieved in this work., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2022 The Authors.)

In this work, the incubation effect on the laser ablation threshold of quartz, after multi-shot irradiation with femtosecond pulses at 1030-nm-wavelength with different repetition rates, was investigated. A strong decrease of the multi-pulse ablation threshold with the number of pulses N was found due to incubation. Moreover, the influence of the repetition rate was negligible in the investigated frequency range which went from 0.06 to 200 kHz. A saturation of the threshold fluence value was observed at number of pulses N > 100 which has been found to be well fitted by an exponential incubation model. Using such model, we estimated the single-pulse ablation threshold value and the incubation coefficient for quartz, which were found equal to Fth,1 = 6.23 ± 0.23 J/cm 2 and k = 0.058 ± 0.004.

A photoacoustic detection module based on a gold-plated photoacoustic cell was reported in this manuscript to measure hydrogen sulfide (H 2 S) gas in sewers. A 1582 nm distributed feedback (DFB) diode laser was employed as the excitation light source of the photoacoustic sensor. Operating pressure within the photoacoustic cell and laser modulation depth were optimized at room temperature, and the long-term stability of the photoacoustic sensor system was analyzed by an Allan-Werle deviation analysis. Experimental results showed that under atmospheric pressure and room temperature conditions, the photoacoustic detection module exhibits a sensitivity of 11.39 μV/ppm of H 2 S and can reach a minimum detection limit (1σ) of 140 ppb of H 2 S with an integration time of 1 s. The sensor was tested for in-field measurements by sampling gas in the sewer near the Shanxi University canteen: levels of H 2 S of 81.5 ppm were measured, below the 100 ppm limit reported by the Chinese sewer bidding document.

We report on a gas sensor based on quartz-enhanced photoacoustic spectroscopy (QEPAS) able to detect multiple gas species for environmental monitoring applications, by exploiting a Vernier effect-based quantum cascade laser as the excitation source. The device emission spectrum consists of ten separated emission clusters covering the range from 2100 up to 2250 cm -1 . Four clusters were selected to detect the absorption features of carbon monoxide (CO), nitrous oxide (N 2 O), carbon dioxide (CO 2 ), and water vapor (H 2 O), respectively. The sensor was calibrated with certified concentrations of CO, N 2 O and CO 2 in a wet nitrogen matrix. The H 2 O absorption feature was used to monitor the water vapor within the gas line during the calibration. Minimum detection limits of 6 ppb, 7 ppb, and 70 ppm were achieved for CO, N 2 O and CO 2 , respectively, at 100 ms of integration time. As proof of concept, the QEPAS sensor was tested by continuously sampling indoor laboratory air and monitoring the analytes concentrations., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2022 The Authors.)

In this Letter, clamp-type quartz tuning fork enhanced photoacoustic spectroscopy (Clamp-type QEPAS) is proposed and realized through the design, realization, and testing of clamp-type quartz tuning forks (QTFs) for photoacoustic gas sensing. The clamp-type QTF provides a wavefront-shaped aperture with a diameter up to 1 mm, while keeping Q factors > 10 4 . This novel, to the best of our knowledge, design results in a more than ten times increase in the area available for laser beam focusing for the QEPAS technique with respect to a standard QTF. The wavefront-shaped clamp-type prongs effectively improve the acoustic wave coupling efficiency. The possibility to implement a micro-resonator system for clamp-type QTF is also investigated. A signal-to-noise enhancement of ∼30 times has been obtained with a single-tube acoustic micro resonator length of 8 mm, ∼20% shorter than the dual-tube micro-resonator employed in a conventional QEPAS system.

In this paper, an ultra-highly sensitive light-induced thermoelastic spectroscopy (LITES) based hydrogen chloride (HCl) sensor, exploiting a custom low-frequency quartz tuning fork (QTF) and a fiber-coupled multi-pass cell (MPC) with optical length of 40 m, was demonstrated. A low resonant frequency of 2.89 kHz of QTF is advantageous to produce a long energy accumulation time in LITES. Furthermore, the use of an MPC with the fiber-coupled structure not only avoids the difficulty in optical alignment but also enhances the system robustness. A distributed feedback (DFB) diode laser emitting at 1.74 µm was used as the excitation source. Under the same operating conditions, the using of low-frequency QTF provided a ~2 times signal improvement compared to that achieved using a standard 32 kHz QTF. At an integration time of 200 ms, a minimum detection limit (MDL) of 148 ppb was achieved. The reported sensor also shows an excellent linear response to HCl gas concentration in the investigated range., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2022 The Authors.)

A sensor system for exhaled ammonia (NH 3 ) monitoring exploiting quartz-enhanced photoacoustic spectroscopy (QEPAS) was demonstrated. An erbium-doped fiber amplifier (EDFA) with an operating frequency band targeting an NH 3 absorption line falling at 1531.68 nm and capable to emit up to 3 W of optical power was employed. A custom T-shaped grooved QTF with prong spacing of 1 mm was designed and realized to allow a proper focusing of the high-power optical beam exiting the EDFA between the prongs. The performance of the realized sensor system was optimized in terms of spectrophone parameters, laser power and modulation current, resulting in a NH 3 minimum detectable concentration of 14 ppb at 1 s averaging time, corresponding to a normalized noise equivalent absorption coefficient (NNEA) of 8.15 × 10 -9 cm -1 W/√Hz. Continuous measurements of the NH 3 level exhaled by 3 healthy volunteers was carried out to demonstrate the potentiality of the developed sensor for breath analysis applications., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2022 The Authors.)

Multi-gas detection represents a suitable solution in many applications, such as environmental and atmospheric monitoring, chemical reaction and industrial process control, safety and security, oil&gas and biomedicine. Among optical techniques, Quartz-Enhanced Photoacoustic Spectroscopy (QEPAS) has been demonstrated to be a leading-edge technology for addressing multi-gas detection, thanks to the modularity, ruggedness, portability and real time operation of the QEPAS sensors. The detection module consists in a spectrophone, mounted in a vacuum-tight cell and detecting sound waves generated via photoacoustic excitation within the gas sample. As a result, the sound detection is wavelength-independent and the volume of the absorption cell is basically determined by the spectrophone dimensions, typically in the order of few cubic centimeters. In this review paper, the implementation of the QEPAS technique for multi-gas detection will be discussed for three main areas of applications: i) multi-gas trace sensing by exploiting non-interfering absorption features; ii) multi-gas detection dealing with overlapping absorption bands; iii) multi-gas detection in fluctuating backgrounds. The fundamental role of the analysis and statistical tools will be also discussed in detail in relation with the specific applications. This overview on QEPAS technique, highlighting merits and drawbacks, aims at providing ready-to-use guidelines for multi-gas detection in a wide range of applications and operating conditions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Author(s). Published by Elsevier B.V. All rights reserved.)

A quartz enhanced photoacoustic spectroscopy (QEPAS) sensor capable to detect high concentrations of methane (C1) and ethane (C2) is here reported. The hydrocarbons fingerprint region around 3 µm was exploited using an interband cascade laser (ICL). A standard quartz tuning fork (QTF) coupled with two resonator tubes was used to detect the photoacoustic signal generated by the target molecules. Employing dedicated electronic boards to both control the laser source and collect the QTF signal, a shoe-box sized QEPAS sensor was realized. All the generated mixtures were downstream humidified to remove the influence of water vapor on the target gases. Several natural gas-like samples were generated and subsequently diluted 1:10 in N 2 . In the concentration ranges under investigation (1%-10% for C1 and 0.1%-1% for C2), both linear and nonlinear responses of the sensor were measured and signal variations due to matrix effects were observed. Partial least squares regression (PLSR) was employed as a multivariate statistical tool to accurately determine the concentrations of C1 and C2 in the mixtures, compensating the matrix relaxation effects. The achieved results extend the range of C1 and C2 concentrations detectable by QEPAS technique up to the percent scale., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2022 The Authors. Published by Elsevier GmbH.)

A compact quartz-enhanced photoacoustic sensor for ppb-level ambient NO 2 detection is demonstrated, in which a high-power blue laser diode module with a small divergence angle was employed to take advantages of the directly proportional relationship between sensitivity and power, hence improving the detection sensitivity. In order to extend the stability time, a custom grooved quartz tuning fork with 800-μm prong spacing is employed to avoid complex signal balance and/or optical spatial filter components. The sensor performance is optimized and assessed in terms of optical coupling, power, gas flow rate, pressure, signal linearity and stability. A minimum detectable concentration (1σ) of 7.3 ppb with an averaging time of 1 s is achieved, which can be further improved to be 0.31 ppb with an averaging time of 590 s. Continuous measurements covering a five-day period are performed to demonstrate the stability and robustness of the reported NO 2 sensor system., Competing Interests: The authors declare that there are no conflicts of interest., (© 2021 The Authors.)

In this paper, an on-beam quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor based on a custom quartz tuning fork (QTF) acting as a photoacoustic transducer, was realized and tested. The QTF is characterized by a resonance frequency of 28 kHz, ~15% lower than that of a commercially available 32.7 kHz standard QTF. One-dimensional acoustic micro resonator (AmR) was designed and optimized by using stainless-steel capillaries. The 28 kHz QTF and AmRs are assembled in on-beam QEPAS configuration. The AmR geometrical parameters have been optimized in terms of length and internal diameter. The laser beam focus position and the AmR coupling distance were also adjusted to maximize the coupling efficiency. For comparison, QEPAS on-beam configurations based on a standard QTF and on the 28 kHz QTF were compared in terms of H 2 O and CO 2 detection sensitivity. In order to better characterize the performance of the system, H 2 O, C 2 H 2 and CO 2 were detected for a long time and the long-term stability was analyzed by an Allan variance analysis. With the integration time of 1 s, the detection limits for H 2 O, C 2 H 2 and CO 2 are 1.2 ppm, 28.8 ppb and 2.4 ppm, respectively. The detection limits for H 2 O, C 2 H 2 and CO 2 can be further improved to 325 ppb, 10.3 ppb and 318 ppb by increasing the integration time to 521 s, 183 s and 116 s., Competing Interests: The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (© 2021 Published by Elsevier GmbH.)

We report on the realization, calibration, and test outdoor of a 19-inches rack 3-units sized Quartz Enhanced Photoacoustic Spectroscopy (QEPAS) trace gas sensor designed for real-time carbon monoxide monitoring in ambient air. Since CO acts as a slow energy relaxer when excited in the mid-infrared spectral region, its QEPAS signal is affected by the presence of relaxation promoters, such as water vapor, or quenchers like molecular oxygen. We analyzed in detail all the CO relaxation processes with typical collisional partners in an ambient air matrix and used this information to evaluate oxygen and humidity-related effects, allowing the real CO concentration to be retrieved. The sensor was tested outdoor in a trafficked urban area for several hours providing results comparable with the daily averages reported by the local air inspection agency, with spikes in CO concentration correlated to the passages of heavy-duty vehicles., Competing Interests: The authors declare that there is no conflict of interest., (© 2021 The Authors.)

In this paper, we report on an ultra-highly sensitive light-induced thermoelastic spectroscopy (LITES)-based carbon monoxide (CO) sensor exploiting custom quartz tuning forks (QTFs) as a photodetector, a multi-pass cell and a mid-infrared quantum cascade laser (QCL) for the first time. The QCL emitting at 4.58 µm with output power of 145 mW was employed as exciting source and the multi-pass cell was employed to increase the gas absorption pathlength. To reduce the noise level, wavelength modulation spectroscopy (WMS) and second harmonic demodulation techniques were exploited. Three QTFs including two custom QTFs (#1 and #2) with different geometries and a commercial standard QTF (#3) were tested as photodetector in the gas sensor. When the integration time of the system was set at 200 ms, minimum detection limits (MDLs) of 750 part-per-trillion (ppt), 4.6 part-per-billion (ppb) and 5.8 ppb were achieved employing QTF #1 #2, and #3, respectively. A full sensor calibration was achieved using the most sensitive QTF#1, demonstrating an excellent linear response with CO concentration.

We report on a comparison between two optical detection techniques, one based on a Quartz-Enhanced Photoacoustic Spectroscopy (QEPAS) detection module, where a quartz tuning fork is acoustically coupled with a pair of millimeter-sized resonator tubes; and the other one based on a Photothermal Spectroscopy (PTS) module where a Fabry-Perot interferometer acts as transducer to probe refractive index variations. When resonant optical absorption of modulated light occurs in a gas sample, QEPAS directly detects acoustic waves while PTS probes refractive index variations caused by local heating. Compact QEPAS and PTS detection modules were realized and integrated in a gas sensor system for detection of carbon monoxide (CO), targeting the fundamental band at 4.6 μm by using a distributed-feedback quantum cascade laser. Performance was compared and ultimate detection limits up to ∼ 6 part-per-billion (ppb) and ∼15 ppb were reached for QEPAS and the PTS module, respectively, using 100 s integration time and 40 mW of laser power., Competing Interests: No conflict of interest, (© 2021 Published by Elsevier GmbH.)

In this work, we report on a quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor for hydrogen sulfide (H 2 S) detection, exploiting a liquid-nitrogen-cooled THz quantum cascade laser (QCL) operating in pulsed mode. The spectrophone was designed to accommodate a THz QCL beam and consisted of a custom quartz tuning fork with a large prong spacing, coupled with acoustic resonator tubes. The targeted rotational transition falls at 2.87 THz (95.626 cm -1 ), with a line-strength of 5.53 ∙ 10 -20 cm/mol. A THz QCL peak power of 150 mW was measured at a heat sink temperature of 81 K, pulse width of 1 μs and repetition rate of 15.8 kHz. A QEPAS record sensitivity for H 2 S detection in the THz range of 360 part-per-billion in volume was achieved at a gas pressure of 60 Torr and 10 s integration time., Competing Interests: The authors declare that there are no conflicts of interest., (© 2020 The Author(s).)

We demonstrated that quartz-enhanced photoacoustic spectroscopy (QEPAS) is an efficient tool to measure the vibrational relaxation rate of gas species, employing quartz tuning forks (QTFs) as sound detectors. Based on the dependence of the QTF resonance frequency on the resonator geometry, a wide range of acoustic frequencies with narrow detection bandwidth was probed. By measuring the QEPAS signal of the target analyte as well as the resonance properties of different QTFs as a function of the gas pressure, the relaxation time can be retrieved. This approach has been tested in the near infrared range by measuring the CH 4 ( nν 4 ) vibrational relaxation rate in a mixture of 1% CH 4 , 0.15 % H 2 O in N 2 , and the H 2 O ( ν 1 ) relaxation rate in a mixture of 0.5 % H 2 O in N 2 . Relaxation times of 3.2 ms Torr and 0.25 ms Torr were estimated for CH 4 and H 2 O, respectively, in excellent agreement with values reported in literature., Competing Interests: The authors declare that there are no conflicts of interest., (© 2020 The Authors.)

We report on a fiber-coupled, quartz-enhanced photoacoustic spectroscopy (QEPAS) near-IR sensor for sequential detection of methane (CH 4 or C1) and ethane (C 2 H 6 or C2) in air. With the aim of developing a lightweight, compact, low-power-consumption sensor suitable for unmanned aerial vehicles (UAVs)-empowered environmental monitoring, an all-fiber configuration was designed and realized. Two laser diodes emitting at 1653.7 nm and 1684 nm for CH 4 and C 2 H 6 detection, respectively, were fiber-combined and fiber-coupled to the collimator port of the acoustic detection module. No cross talk between methane and ethane QEPAS signal was observed, and the related peak signals were well resolved. The QEPAS sensor was calibrated using gas samples generated from certified concentrations of 1% CH 4 in N 2 and 1% C 2 H 6 in N 2 . At a lock-in integration time of 100 ms, minimum detection limits of 0.76 ppm and 34 ppm for methane and ethane were achieved, respectively. The relaxation rate of CH 4 in standard air has been investigated considering the effects of H 2 O, N 2 and O 2 molecules. No influence on the CH 4 QEPAS signal is expected when the water vapor concentration level present in air varies in the range 0.6-3%.

An optical sensor for highly sensitive detection of carbon monoxide (CO) in sulfur hexafluoride (SF 6 ) was demonstrated by using the quartz-enhanced photoacoustic spectroscopy technique. A spectrophone composed of a custom 8 kHz T-shaped quartz tuning fork with grooved prongs and a pair of resonator tubes, to amplify the laser-induced acoustic waves, was designed aiming to maximize the CO photoacoustic response in SF 6 . A theoretical analysis and an experimental investigation of the influence of SF 6 gas matrix on spectrophone resonance properties for CO detection have been provided, and the performances were compared with the standard air matrix. A mid-infrared quantum cascade laser with a central wavelength at 4.61 μm, resonant with the fundamental band of CO, and an optical power of 20 mW was employed as the light excitation source. A minimum detection limit of 10 ppb at 10 s of integration time was achieved, and a sensor response time of ∼3 min was measured.

An ultra-highly sensitive and robust CH 4 sensor is reported based on a 3.3 µm interband cascade laser (ICL) and a low-noise differential photoacoustic (PAS) cell. The ICL emission wavelength targeted a fundamental absorption line of CH 4 at 2988.795 cm -1 with an intensity of 1.08 × 10 -19 cm/molecule. The double-pass and differential design of the PAS cell effectively enhanced the PAS signal amplitude and decreased its background noise. The wavelength modulation depth, operating pressure and V-T relaxation promotion were optimized to maximize the sensor detection limit. With an integration time of 90 s, a detection limit of 0.6 ppb was achieved. No additional water or air laser cooling were required and thereby allowing the realization of a compact and robust CH 4 sensor.

We report on a study of light-induced thermo-elastic effects occurring in quartz tuning forks (QTFs) when exploited as near-infrared light detectors in a tunable diode laser absorption spectroscopy sensor setup. Our analysis showed that when the residual laser beam transmitted by the absorption cell is focused on the QTF surface area where the maximum strain field occurs, the QTF signal-to-noise ratio (SNR) is proportional to the strain itself and to the QTF accumulation time. The SNR was also evaluated when the pressure surrounding the QTF was lowered from 700 Torr to 5 Torr, resulting in an enhancement factor of ∽4 at the lowest pressure. At 5 torr, the QTF employed as light detector showed an SNR ∽6.5 times higher than that obtained by using a commercially available amplified photodetector.

A dual-gas sensor based on the combination of a quartz-enhanced photoacoustic spectroscopy (QEPAS) sensor and an electronic hygrometer was realized for the simultaneous detection of methane (CH 4 ) and water vapor (H 2 O) in air. The QEPAS sensor employed an interband cascade laser operating at 3.34 μm capable of targeting a CH 4 absorption line at 2988.8 cm -1 and a water line at 2988.6 cm -1 . Water vapor was measured with both the electronic hygrometer and the QEPAS sensor for comparison. The measurement accuracy provided by the hygrometer enabled the adjustment of methane QEPAS signal with respect to the water vapor concentration to retrieve the actual CH 4 concentration. The sensor was tested by performing prolonged measurements of CH 4 and H 2 O over 60 h to demonstrate the effectiveness of this approach for environmental monitoring applications.

We report on a comparison between piezoelectric and interferometric readouts of vibrations in quartz tuning forks (QTFs) when acting as sound wave transducers in a quartz-enhanced photoacoustic setup (QEPAS) for trace gas detection. A theoretical model relating the prong vibration amplitude with the QTF prong sizes and electrical resistance is proposed. To compare interferometric and piezoelectric readouts, two QTFs have been selected; a tuning fork with rectangular-shape of the prongs, having a resonance frequency of 3.4 kHz and a quality-factor of 4,000, and a QTF with prong having a T-shape characterized by a resonance frequency of 12.4 kHz with a quality-factor of 15,000. Comparison between the interferometric and piezoelectric readouts were performed by using both QTFs in a QEPAS sensor setup for water vapor detection. We demonstrated that the QTF geometry can be properly designed to enhance the signal from a specific readout mode., (© 2019 The Author(s).)

Here we report on the broadband detection of nitrous oxide (N 2 O) and methane (CH 4 ) mixtures in dry nitrogen by using a quartz-enhanced photoacoustic (QEPAS) sensor exploiting an array of 32 distributed-feedback quantum cascade lasers, within a spectral emission range of 1190-1340 cm -1 as the excitation source. Methane detection down to a minimum detection limit of 200 ppb at 10 s lock-in integration time was achieved. The sensor demonstrated a linear response in the range of 200-1000 ppm. Three different mixtures of N 2 O and CH 4 in nitrogen at atmospheric pressure have been analyzed. The capability of the developed QEPAS sensor to selectively determine the N 2 O and CH 4 concentrations was demonstrated, in spite of significant overlap in their respective absorption spectra in the investigated spectral range., (© 2020 The Authors.)

A grooved quartz tuning fork (QTF) with a prong spacing of 800 µm for QEPAS application is reported. The prongs spacing is large enough to facilitate optical alignments when a degraded laser beam is used for QEPAS-based trace gas sensors. The grooved QTF has a resonance frequency of 15.2 kHz at atmospheric pressure and is characterized by four rectangular grooves carved on the QTF prong surfaces. With a grooved-prong, the electrical resistance R of the QTF is reduced resulting in an enhanced piezoelectric signal, while the Q factor is not affected, remaining as high as 15000 at atmospheric pressure. The geometric parameters of the acoustic micro resonators (AmRs) for on-beam QEPAS were optimized to match the grooved QTF, and a signal-to-noise gain factor of ∼ 30 was obtained with an optimum configuration. The performance of the QEPAS-based sensor was demonstrated exploiting an interband cascade laser (ICL) for CH 4 detection and a 1σ normalized noise equivalent absorption (NNEA) coefficient of 4.1×10 -9 cm -1 W/√Hz was obtained at atmospheric pressure.

A theoretical model describing the acoustic coupling between two resonator tubes in spectrophones exploiting custom-made quartz tuning forks (QTFs) is proposed. The model is based on an open-end correction to predict the optimal tube length. A calculation of the sound field distribution from one tube exit allowed for the estimation of the optimal radius as a function of the QTF prong spacing and the sound wavelength. The theoretical predictions have been confirmed using experimental studies employing a custom QTF with a fundamental flexural mode resonance frequency of 15.8 kHz and a quality factor of 15,000 at atmospheric pressure. The spacing between the two prongs was 1.5 mm. Spectrophones mounting this QTF were implemented for the quartz-enhanced photoacoustic detection of water vapor in air in the mid-infrared spectral range.

A detailed investigation of the influence of quartz tuning forks (QTFs) resonance properties on the performance of quartz-enhanced photoacoustic spectroscopy (QEPAS) exploiting QTFs as acousto-electric transducers is reported. The performance of two commercial QTFs with the same resonance frequency (32.7 KHz) but different geometries and two custom QTFs with lower resonance frequencies (2.9 KHz and 7.2 KHz) were compared and discussed. The results demonstrated that the fundamental resonance frequency as well as the quality factor and the electrical resistance were strongly inter-dependent on the QTF prongs geometry. Even if the resonance frequency was reduced, the quality factor must be kept as high as possible and the electrical resistance as low as possible in order to guarantee high QEPAS performance.

We demonstrated a versatile and innovative gas sensing system based on a Fabry-Pérot (FP) filter detector, which operates in the spectral range from 3.1 to 4.4μm (3226-2273cm -1 ) with a spectral resolution of 20nm. The developed sensor system can be used to record the entire spectrum by means of a one-time scan or, alternatively, to access selected spectral regions by using the tunable FP filter detector. A multipass cell with an effective path length of 2.5m was implemented to improve the detection sensitivity. The spectra of methane, formaldehyde and carbon dioxide were simultaneously measured, with detection limits of 200ppm, 900ppm and 20ppm, respectively. A seven-day continuous measurement for indoor carbon dioxide gas was carried out demonstrating the stability and robustness of the reported sensor system., (Copyright © 2019. Published by Elsevier B.V.)

The design and realization of two highly sensitive and easily interchangeable spectrophones based on custom quartz tuning forks, with a rectangular (S 1 ) or T-shaped (S 2 ) prongs geometry, is reported. The two spectrophones have been implemented in a QEPAS sensor for ethylene detection, employing a DFB-QCL emitting at 10.337 μm with an optical power of 74.2 mW. A comparison between their performances showed a signal-to-noise ratio 3.4 times higher when implementing the S 2 spectrophone. For the S 2 -based sensor, a linear dependence of the QEPAS signal on ethylene concentration was demonstrated in the 5 ppm -100 ppm range. For a 10 s lock-in integration time, an ethylene minimum detection limit of 10 ppb was calculated.

We report on the design, realization, and performance of novel quartz tuning forks (QTFs) optimized for quartz-enhanced photoacoustic spectroscopy (QEPAS). Starting from a QTF geometry designed to provide a fundamental flexural in-plane vibrational mode resonance frequency of ~16 kHz, with a quality factor of 15,000 at atmospheric pressure, two novel geometries have been realized: a QTF with T-shaped prongs and a QTF with prongs having rectangular grooves carved on both surface sides. The QTF with grooves showed the lowest electrical resistance, while the T-shaped prongs QTF provided the best photoacoustic response in terms of signal-to-noise ratio (SNR). When acoustically coupled with a pair of micro-resonator tubes, the T-shaped QTF provides a SNR enhancement of a factor of 60 with respect to the bare QTF, which represents a record value for mid-infrared QEPAS sensing.